organic compounds
2,2′-[4-Acetyl-1,3-phenylenebis(oxy)]diacetic acid
aSchool of Chemistry & Environmental Engineering, Jiujiang University, Jiujiang 332005, People's Republic of China
*Correspondence e-mail: jgwang117@163.com
In the title compound, C12H12O7, the dihedral angles between the benzene ring and the mean planes of the 3-carboxymethoxy, 1-carboxymethoxy and acetyl substituents are 8.67 (7), 7.81 (6) and 10.3 (18)°, respectively. In the crystal, molecules are linked by typical carboxylic acid O—H⋯O hydrogen bonds, forming a zigzag chain. C—H⋯O interactions also occur.
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812047897/go2075sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047897/go2075Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812047897/go2075Isup3.cml
2,4-dihydroxyacetophenone (10.64 g, 0.07 mol) and potassium hydroxide (10.58 g, 0.189 mol) were dissolved in dry acetone (100 ml) in a three-neck flask. Then ethyl bromoacetate (28.06 g, 0.168 mol) was dropwise added at room temperature and vigorously stirred for 3 h. The progress of the reaction was monitored by TCL (Si gel, developing solvent V (acetone) /V (petroleum ether) = 1:2). After suction filtration and distillation to remove the solvent, a white solid was obtained, 19.76 g, yield 87.1%. This solid was dissolved in acetone (30 ml) and 20% aq. NaOH (50 ml) was added. The reaction mixture was stirred at 323 K for 1.5 h. After acidifying the misxture with dilute hydrochloric acid to pH=3, followed by suction filtrationand washing the residue with water, the target product was prepared. After recrystallization from ethanol, crystalline colorless needles were obtained.
All the carbon-bounded hydrogen atoms were located at their ideal positions with the C—H=0.93 Å, C—H=0.96 Å, C—H=0.97 Å and Uiso(H)=1.2Ueq(C). All the hydrogen atoms bonded to the oxygen atoms were located from the difference maps and refined with the restraints of O—H=0.82 (1) Å and Uiso(H)=1.5Ueq(O).
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C12H12O7 | Z = 2 |
Mr = 268.22 | F(000) = 280 |
Triclinic, P1 | Dx = 1.508 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.1351 (6) Å | Cell parameters from 3359 reflections |
b = 7.8346 (9) Å | θ = 2.6–31.8° |
c = 15.6157 (18) Å | µ = 0.13 mm−1 |
α = 86.217 (2)° | T = 298 K |
β = 81.321 (1)° | Block, colourless |
γ = 72.101 (2)° | 0.12 × 0.10 × 0.10 mm |
V = 590.86 (12) Å3 |
Bruker APEXII CCD diffractometer | 2049 independent reflections |
Radiation source: fine-focus sealed tube | 1860 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −6→6 |
Tmin = 0.985, Tmax = 0.987 | k = −9→9 |
3902 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0795P)2 + 0.1078P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2049 reflections | Δρmax = 0.24 e Å−3 |
176 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.036 (8) |
C12H12O7 | γ = 72.101 (2)° |
Mr = 268.22 | V = 590.86 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.1351 (6) Å | Mo Kα radiation |
b = 7.8346 (9) Å | µ = 0.13 mm−1 |
c = 15.6157 (18) Å | T = 298 K |
α = 86.217 (2)° | 0.12 × 0.10 × 0.10 mm |
β = 81.321 (1)° |
Bruker APEXII CCD diffractometer | 2049 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1860 reflections with I > 2σ(I) |
Tmin = 0.985, Tmax = 0.987 | Rint = 0.016 |
3902 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2049 reflections | Δρmin = −0.23 e Å−3 |
176 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.9386 (3) | 0.64900 (17) | 0.22991 (8) | 0.0282 (3) | |
C2 | 0.6877 (3) | 0.75023 (17) | 0.27294 (9) | 0.0291 (3) | |
H2 | 0.6254 | 0.8735 | 0.2630 | 0.035* | |
C3 | 0.5297 (3) | 0.66705 (18) | 0.33088 (9) | 0.0290 (3) | |
C4 | 0.6221 (3) | 0.48246 (18) | 0.34697 (9) | 0.0332 (3) | |
H4 | 0.5166 | 0.4266 | 0.3858 | 0.040* | |
C5 | 0.8736 (3) | 0.38464 (17) | 0.30388 (9) | 0.0329 (3) | |
H5 | 0.9361 | 0.2618 | 0.3152 | 0.040* | |
C6 | 1.0383 (3) | 0.46109 (17) | 0.24430 (9) | 0.0299 (3) | |
C7 | 1.0249 (3) | 0.90973 (18) | 0.15901 (10) | 0.0349 (3) | |
H7A | 1.0211 | 0.9696 | 0.2118 | 0.042* | |
H7B | 0.8424 | 0.9519 | 0.1412 | 0.042* | |
C8 | 1.2360 (3) | 0.94824 (18) | 0.08886 (9) | 0.0329 (3) | |
C9 | 0.1228 (3) | 0.70250 (18) | 0.43152 (9) | 0.0323 (3) | |
H9A | 0.2214 | 0.6572 | 0.4806 | 0.039* | |
H9B | 0.0869 | 0.6029 | 0.4068 | 0.039* | |
C10 | −0.1449 (3) | 0.84177 (18) | 0.46089 (9) | 0.0321 (3) | |
C11 | 1.3024 (3) | 0.33765 (19) | 0.20074 (10) | 0.0363 (3) | |
C12 | 1.4694 (4) | 0.3989 (2) | 0.12491 (12) | 0.0524 (5) | |
H12A | 1.6153 | 0.2977 | 0.1007 | 0.079* | |
H12B | 1.5473 | 0.4845 | 0.1436 | 0.079* | |
H12C | 1.3527 | 0.4537 | 0.0818 | 0.079* | |
O1 | 1.1504 (2) | 1.10815 (14) | 0.05426 (8) | 0.0472 (3) | |
H1 | 1.2707 | 1.1235 | 0.0164 | 0.071* | |
O2 | 1.4614 (2) | 0.84065 (14) | 0.06836 (7) | 0.0463 (3) | |
O3 | 1.1036 (2) | 0.72247 (13) | 0.17277 (7) | 0.0406 (3) | |
O4 | 0.28549 (19) | 0.77925 (13) | 0.36867 (7) | 0.0369 (3) | |
O5 | −0.2075 (2) | 0.99593 (13) | 0.43053 (7) | 0.0421 (3) | |
O6 | −0.2994 (2) | 0.78060 (14) | 0.51955 (8) | 0.0487 (3) | |
H6 | −0.4400 | 0.8616 | 0.5357 | 0.073* | |
O7 | 1.3789 (3) | 0.18327 (14) | 0.22649 (9) | 0.0579 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0251 (6) | 0.0269 (6) | 0.0304 (6) | −0.0088 (5) | 0.0037 (5) | 0.0021 (5) |
C2 | 0.0258 (7) | 0.0232 (6) | 0.0344 (7) | −0.0059 (5) | 0.0025 (5) | 0.0039 (5) |
C3 | 0.0231 (6) | 0.0288 (7) | 0.0317 (7) | −0.0059 (5) | 0.0019 (5) | 0.0009 (5) |
C4 | 0.0300 (7) | 0.0300 (7) | 0.0372 (7) | −0.0111 (5) | 0.0041 (6) | 0.0061 (5) |
C5 | 0.0315 (7) | 0.0233 (6) | 0.0408 (8) | −0.0071 (5) | 0.0005 (6) | 0.0034 (5) |
C6 | 0.0279 (7) | 0.0247 (7) | 0.0344 (7) | −0.0065 (6) | 0.0003 (5) | −0.0003 (5) |
C7 | 0.0299 (7) | 0.0264 (7) | 0.0420 (8) | −0.0064 (5) | 0.0089 (6) | 0.0039 (6) |
C8 | 0.0306 (7) | 0.0283 (7) | 0.0375 (7) | −0.0101 (6) | 0.0031 (6) | 0.0028 (5) |
C9 | 0.0266 (7) | 0.0322 (7) | 0.0342 (7) | −0.0087 (6) | 0.0057 (5) | 0.0036 (6) |
C10 | 0.0292 (7) | 0.0322 (7) | 0.0328 (7) | −0.0105 (6) | 0.0051 (5) | −0.0010 (5) |
C11 | 0.0314 (7) | 0.0283 (7) | 0.0448 (8) | −0.0061 (6) | 0.0033 (6) | −0.0045 (6) |
C12 | 0.0432 (9) | 0.0373 (8) | 0.0602 (10) | −0.0011 (7) | 0.0226 (8) | −0.0061 (7) |
O1 | 0.0391 (6) | 0.0365 (6) | 0.0568 (7) | −0.0098 (5) | 0.0118 (5) | 0.0142 (5) |
O2 | 0.0342 (6) | 0.0394 (6) | 0.0540 (7) | −0.0066 (5) | 0.0142 (5) | 0.0094 (5) |
O3 | 0.0337 (6) | 0.0259 (5) | 0.0518 (6) | −0.0064 (4) | 0.0185 (4) | 0.0047 (4) |
O4 | 0.0270 (5) | 0.0298 (5) | 0.0446 (6) | −0.0047 (4) | 0.0126 (4) | 0.0052 (4) |
O5 | 0.0344 (6) | 0.0333 (6) | 0.0508 (6) | −0.0076 (4) | 0.0102 (5) | 0.0047 (4) |
O6 | 0.0371 (6) | 0.0384 (6) | 0.0574 (7) | −0.0071 (5) | 0.0228 (5) | 0.0052 (5) |
O7 | 0.0491 (7) | 0.0285 (6) | 0.0774 (9) | 0.0037 (5) | 0.0135 (6) | 0.0050 (5) |
C1—O3 | 1.3596 (16) | C8—O2 | 1.2154 (18) |
C1—C2 | 1.3862 (19) | C8—O1 | 1.3033 (17) |
C1—C6 | 1.4170 (18) | C9—O4 | 1.4166 (15) |
C2—C3 | 1.3884 (18) | C9—C10 | 1.4979 (19) |
C2—H2 | 0.9300 | C9—H9A | 0.9700 |
C3—O4 | 1.3642 (17) | C9—H9B | 0.9700 |
C3—C4 | 1.3949 (19) | C10—O5 | 1.2323 (17) |
C4—C5 | 1.381 (2) | C10—O6 | 1.2863 (17) |
C4—H4 | 0.9300 | C11—O7 | 1.2126 (18) |
C5—C6 | 1.3927 (19) | C11—C12 | 1.496 (2) |
C5—H5 | 0.9300 | C12—H12A | 0.9600 |
C6—C11 | 1.4966 (19) | C12—H12B | 0.9600 |
C7—O3 | 1.4079 (16) | C12—H12C | 0.9600 |
C7—C8 | 1.5050 (18) | O1—H1 | 0.8200 |
C7—H7A | 0.9700 | O6—H6 | 0.8200 |
C7—H7B | 0.9700 | ||
O3—C1—C2 | 122.68 (11) | O2—C8—C7 | 122.72 (12) |
O3—C1—C6 | 116.25 (11) | O1—C8—C7 | 112.58 (12) |
C2—C1—C6 | 121.06 (12) | O4—C9—C10 | 109.47 (11) |
C1—C2—C3 | 119.83 (11) | O4—C9—H9A | 109.8 |
C1—C2—H2 | 120.1 | C10—C9—H9A | 109.8 |
C3—C2—H2 | 120.1 | O4—C9—H9B | 109.8 |
O4—C3—C2 | 114.79 (11) | C10—C9—H9B | 109.8 |
O4—C3—C4 | 124.56 (12) | H9A—C9—H9B | 108.2 |
C2—C3—C4 | 120.65 (12) | O5—C10—O6 | 124.81 (13) |
C5—C4—C3 | 118.49 (12) | O5—C10—C9 | 122.91 (12) |
C5—C4—H4 | 120.8 | O6—C10—C9 | 112.28 (11) |
C3—C4—H4 | 120.8 | O7—C11—C12 | 119.44 (13) |
C4—C5—C6 | 123.14 (12) | O7—C11—C6 | 118.94 (13) |
C4—C5—H5 | 118.4 | C12—C11—C6 | 121.60 (12) |
C6—C5—H5 | 118.4 | C11—C12—H12A | 109.5 |
C5—C6—C1 | 116.82 (12) | C11—C12—H12B | 109.5 |
C5—C6—C11 | 117.25 (11) | H12A—C12—H12B | 109.5 |
C1—C6—C11 | 125.93 (12) | C11—C12—H12C | 109.5 |
O3—C7—C8 | 106.80 (11) | H12A—C12—H12C | 109.5 |
O3—C7—H7A | 110.4 | H12B—C12—H12C | 109.5 |
C8—C7—H7A | 110.4 | C8—O1—H1 | 109.5 |
O3—C7—H7B | 110.4 | C1—O3—C7 | 119.30 (10) |
C8—C7—H7B | 110.4 | C3—O4—C9 | 117.02 (10) |
H7A—C7—H7B | 108.6 | C10—O6—H6 | 109.5 |
O2—C8—O1 | 124.70 (13) | ||
O3—C1—C2—C3 | −179.66 (12) | O3—C7—C8—O1 | 163.06 (12) |
C6—C1—C2—C3 | −0.3 (2) | O4—C9—C10—O5 | 2.36 (19) |
C1—C2—C3—O4 | −179.26 (11) | O4—C9—C10—O6 | −178.61 (11) |
C1—C2—C3—C4 | 0.6 (2) | C5—C6—C11—O7 | −9.3 (2) |
O4—C3—C4—C5 | 179.78 (12) | C1—C6—C11—O7 | 171.32 (14) |
C2—C3—C4—C5 | −0.1 (2) | C5—C6—C11—C12 | 168.98 (14) |
C3—C4—C5—C6 | −0.8 (2) | C1—C6—C11—C12 | −10.4 (2) |
C4—C5—C6—C1 | 1.1 (2) | C2—C1—O3—C7 | 2.9 (2) |
C4—C5—C6—C11 | −178.34 (13) | C6—C1—O3—C7 | −176.45 (12) |
O3—C1—C6—C5 | 178.87 (12) | C8—C7—O3—C1 | −176.25 (11) |
C2—C1—C6—C5 | −0.52 (19) | C2—C3—O4—C9 | −176.96 (11) |
O3—C1—C6—C11 | −1.8 (2) | C4—C3—O4—C9 | 3.1 (2) |
C2—C1—C6—C11 | 178.85 (12) | C10—C9—O4—C3 | −175.88 (11) |
O3—C7—C8—O2 | −17.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.83 | 2.6530 (14) | 180 |
O6—H6···O5ii | 0.82 | 1.83 | 2.6352 (15) | 167 |
C2—H2···O7iii | 0.93 | 2.44 | 3.3566 (17) | 168 |
C4—H4···O6iv | 0.93 | 2.52 | 3.4392 (19) | 169 |
Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x−1, −y+2, −z+1; (iii) x−1, y+1, z; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H12O7 |
Mr | 268.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 5.1351 (6), 7.8346 (9), 15.6157 (18) |
α, β, γ (°) | 86.217 (2), 81.321 (1), 72.101 (2) |
V (Å3) | 590.86 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.12 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.985, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3902, 2049, 1860 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.120, 1.05 |
No. of reflections | 2049 |
No. of parameters | 176 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.23 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.83 | 2.6530 (14) | 180 |
O6—H6···O5ii | 0.82 | 1.83 | 2.6352 (15) | 167 |
C2—H2···O7iii | 0.93 | 2.44 | 3.3566 (17) | 168 |
C4—H4···O6iv | 0.93 | 2.52 | 3.4392 (19) | 169 |
Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x−1, −y+2, −z+1; (iii) x−1, y+1, z; (iv) −x, −y+1, −z+1. |
Acknowledgements
This study was funded by Jiangxi Provincial Department of Education (GJJ08433) and the Doctoral Research Initiating Project of Jiujiang University.
References
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, C., Li, H., Liu, D. & Liu, M. (2007). Acta Cryst. E63, o4210. Web of Science CSD CrossRef IUCr Journals Google Scholar
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The title compound is a potential inhibitor of mushroom tyrosinase.
The dihedral angles between the mean planes of the benzene ring and those of the 2-carboxymethoxyl,(O1-C8-C7-O3-O2), 4-carboxymethoxyl (O6-C10-C9-O4-O5), and acetyl, (C11-C12-O7), substituents are 8.67 (7)°, 7.81 (6)°, and 10.3 (18)° respectively.
In the crystal, the molecules are linked by typical carboxylic acid O—H···O hydrogen bonding forming a one-dimensional zig-zag chain Table 1, Figure 2.
This chain is linked to anti-parallel chains by C—H···O weak hydrogen bonds to form a two dimensional sheet stabilizing the supramolecular structure, Table 1, Figure 2.